The present invention relates to liquid formulations comprising microbicidally active ingredients and to the use of these formulations as microbicidally active ingredient in cosmetic products, household articles or hand disinfectants and to the use as preservatives in household articles and cosmetic products.
The present invention relates to concentrated liquid formulations (a) comprising
(a1) 1 to 80% by weight of a microbicidally active ingredient,
(a2) 20 to 99% by weight of a mono- or dihydric alcohol or mixtures thereof, and
concentrated liquid formulations (b) comprising
(b1) 5.1 to 30% by weight of a microbicidally active ingredient,
(b2) 0 to 80% by weight of a sulfonate,
(b3) 1 to 60% by weight of a C1-C11monocarboxylic acid or of a C3-C12di- or -polycarboxylic acid;
(b4) 0 to 90% by weight of a mono- or dihydric alcohol or mixtures thereof, and
water to 100%, it always being necessary for one of the components (b2) or (b4) to be present.
The liquid formulation (a) preferably comprises
(a1) 20 to 70% by weight of a microbicidally active ingredient and
(a2) 30 to 80% by weight of a mono- or dihydric alcohol or mixtures thereof.
Formulation (b) prefer ably comprises
(b1) 10 to 30% by weight of a microbicidally active ingredient,
(b2) 0 to 80% by weight of a sulfonate,
(b3) 1 to 60% by weight of a C1-C11monocarboxylic acid or of a C3-C12di- or -polycarboxylic acid;
(b4) 0 to 90% by weight of a mono- or dihydric alcohol or mixtures thereof, and
water to 100%.
Component (a1) or (b1) is, in particular, 2-hydroxydiphenyl ether, of the formula 
in which
Y is chlorine or bromine,
Z is SO2H, NO2 or C1-C4alkyl,
r is 0 to 3,
o is 0 to 3,
p is 0 or 1,
m is 0 or 1 and
n is 0 or 1.
Especially interesting compounds of the formula (1) are those in which
Y is chlorine or bromine,
m is 0,
n is 0 or 1,
o is 1 or 2,
r is 1 or 2 and
p is 0.
Very especially interesting compounds of the formula (1) are those in which
Y is chlorine,
m is 0,
n is 0,
o is 1,
r is 2 and
p is 0.
Very especially preferred is the compound of the formula 
Other suitable microbicidally active ingredients which correspond to component (a1) or (b1) are
phenol derivatives,
diphenyl compounds,
benzyl alcohols,
chlorhexidine,
C12-C14alkylbetaines and C8-C18fatty acid amido alkylbetaines,
amphoteric surfactants,
trihalocarbanilides and
quaternary ammonium salts.
The phenol derivatives are preferably compounds of the formula 
in which
R1 is hydrogen, hydroxyl, C1-C4alkyl, chlorine, nitro, phenyl or benzyl,
R2 is hydrogen, hydroxyl, C1-C6alkyl or halogen,
R3 is hydrogen, C1-C6alkyl, hydroxyl, chlorine, nitro or a sulfur in the form of its alkali metal salts or ammonium salts,
R4 is hydrogen or methyl and
R5 is hydrogen or nitro.
Halogen is bromine or, preferably, chlorine.
Examples of such compounds are chlorophenols (o-, m-, p-), 2,4-dichlorophenol, p-nitrophenol, picric acid, xylenol, p-chloro-m-xylenol, cresols (o-, m-, p-), p-chloro-m-cresol, pyrocatechol, resorcinol, 4-n-hexylresorcinol, pyrogallol, phloroglucin, carvacrol, thymol, p-chlorothymol, o-phenylphenol, o-benzylphenol, p-chloro-o-benzylphenol and 4-phenolsulfonic acid.
The diphenyl compounds are preferably compounds of the formula 
in which
X is sulfur or the methylene group,
R1 and Rxe2x80x21 are hydroxyl and
R2, Rxe2x80x22, R3, Rxe2x80x23, R4, Rxe2x80x24, R5 and Rxe2x80x25 independently of one another, are hydrogen or halogen.
Examples of compounds of the formula (4) are hexachlorophene, tetrachlorophene, dichlorophene, 2,3-dihydroxy-5,5xe2x80x2-dichlorodiphenyl sulfide, 2,2xe2x80x2-dihydroxy-3,3xe2x80x2,5,5xe2x80x2-tetrachlorodiphenyl sulfide, 2,2xe2x80x2-dihydroxy-3,3xe2x80x2,5,5xe2x80x2,6,6xe2x80x2-hexachlorodiphenyl sulfide and 3,3xe2x80x2-dibromo-5,5xe2x80x2-dichloro-2,2xe2x80x2-dihydroxydiphenylamine.
The benzyl alcohols are preferably those of the formula 
in which
R1, R2, R3, R4 and R5, independently of one another, are hydrogen or chlorine.
Examples of compounds of the formula (5) are benzyl alcohol, 2,4-, 3,5- or 2,6-dichlorobenzyl alcohol and trichlorobenzyl alcohol.
Chlorhexidine can be employed as such or in the form of its salt with organic and inorganic acids.
An example which may be mentioned of C8-C18fatty acid amidoalkylbetaine is coconut fatty add C8-C18amidopropylbetaine.
Examples of suitable amphoteric surfactants are C12alkylamino-, C1-C3alkanecarboxylic acids, for example alkylaminoacetic acids or alkylaminopropionic acids.
Trihalocarbanilides are, in particular, those of the formula 
in which
Hal is chlorine or bromine,
n and m are 1 or 2 and
n+m are 3.
The quaternary ammonium salts are, in particular, those of the formula 
in which
R7, R8, and R9 and R10, independently of one another, are C1-C18 alkyl,
C1-C18alkoxy or phenyl-C1-C5alkyl and
Hal is chlorine or bromine.
Very especially preferred is the compound of the formula 
in which
n is a number from 7 to 17.
Monohydic alcohols corresponding to component (a2) or (b4) are linear or branched C2-C18alcohols, for example ethanol, n-propanol, isopropanol, butanol, lauryl alcohol, caryl alcohol, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C9-C11oxo alcohol, tridecyl alcohol, isotridecyl alcohol or linear primary alcohols ((copyright)Alfol types) having 8 to 18 carbon atoms. Some representatives of these Alfol types are (copyright)Alfol (8-10), (copyright)Alfol (9-11), (copyright)Alfol (10-14), (copyright)Alfol (12-13) or (copyright)Alfol (16-18).
Other substances which are preferably employed in the liquid formulations according to the invention are monohydric alcohols of the general formula 
in which
X is a halogen atom
Y is a radical of the formula xe2x80x94Oxe2x80x94(CH2)mxe2x80x94 or xe2x80x94CH2xe2x80x94 or a direct bond;
n is 0 to 5; and
m is 1 to 3.
Preferred compounds of the formula (9) are those in which
Y is xe2x80x94Oxe2x80x94(CH2)mxe2x80x94 and
n=0.
If dihydric alcohols are employed as component (a2), these have, in particular, 2 to 6 carbon atoms in the alkyl moiety, for example ethylene glycol, 1,2- or 1,3-propanediol, 1,3-, 1,4- or 2,3-butanediol, 1,5-pentanediol and 1,6-hexanediol. 1,2-Propanediol (propylene glycol) is preferred.
Suitable sulfonates (component (b2)) are, in particular, their salts of terpenoids, or mono- or binuclear aromatic compounds, for example sulfonates of camphor, toluene, xylene, cumene or naphthol.
Suitable examples of component (b3) as saturated or unsaturated C3-C12di- or polycarboxylic acids are malonic, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, undecane- and dodecanedicarboxylic acid, fumaric acid, maleic acid, tartaric acid and maleic acid, hydroxyacetic acid (glycolic acid), xc3xa1-hydroxypropionic acid (lactic acid), and citric and aconitic acid.
Examples of aliphatic saturated or unsaturated C1-C11monocarboxylic acids are acetic acid, propionic acid, caproic acid, capric acid and undecylenoic acid.
Other suitable substances are aminocarboxylic acids, such as ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetetraacetic acid and nitrilotriacetic acid; cycloaliphatic carboxylic acids, such as camphoric acid; aromatic carboxylic acids, such as benzoic acid, phenylacetic acid, phenoxyacetic acid and zimanic acid, 2-, 3- and 4-hydroxybenzoic acid, anilic acid, and o-, m- and p-chlorophenylacetic acid and o-, m- and p-chlorophenoxyacetic acid; alkali metal salts and amine salts of inorganic acids, such as the sodium salts, potassium salts and amine(R1R2R3) salts of hydrochloric acid, sulfuric acid, phosphoric acid, C1-C10alkylphosphoric acid and boric acid, R1, R2 and R3 having the abovementioned meanings; isethionic acid; tannic acid; and acid amides of the formula 
in which
R1 is hydrogen or C1-C12alkyl and
R2 and R3 independently of one another are hydrogen, C1-C12alkyl, C2-C12alkenyl,
C1-C12hydroxyalkenyl, C2-C12hydroxyalkyl; or a polyglycol ether chain having 1 to 30 groups xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94 or xe2x80x94CHY1xe2x80x94CHY2xe2x80x94Oxe2x80x94, where
Y1 or Y2 is one hydrogen radical, the other being methyl, for example N-methylacetamide.
All carboxylic acids corresponding to component (b3) which are employed in accordance with the invention can also preferably be employed in the form of their water-soluble alkali metal salts or ammonium salts.
Preferred liquid formulations (a) according to the invention comprise
(a1) 20 to 70, preferably 30 to 60, % by weight of a microbicidally active ingredient of the formula (1) and
(a2) 30 to 80, preferably 40 to 70, % by weight of a mono- or dihydric alcohol or mixtures thereof.
Very especially preferred are formulations which comprise, as component (a2), the compound of the formula (9) as monohydric alcohol, and/or a dihydric alcohol which has 2 to 6 carbon atoms in the alkyl moiety.
Formulations which are preferably employed from amongst the above are formulations which comprise either a monohydric alcohol or a dihydric alcohol. In particular, a suitable monohydric alcohol is phenoxyethanol and a suitable dihydric alcohol 1,2-propanediol.
Preferred liquid formulations (b) comprise
(b1) 10 to 30, preferably 15 to 25, % by weight of a microbicidally active ingredient of the formula (1),
(b2) 0 to 80, preferably 10 to 70, % by weight of a sulfonate,
(b3) 1 to 60, preferably 10 to 50, % by weight of a C1-C11monocarboxylic acid or of a C3-C12di- or -polycarboxylic acid; and
(b4) 0 to 90, preferably 5 to 75, % by weight of a mono- or dihydric alcohol, and water to 100%,
it always being necessary for one of components (b2) or (b4) to be present.
Very especially preferred liquid formulations (b) are those which comprise cumenesulfonate as component (b2), a hydroxyacid as component (b3) and a dihydric alcohol having 2 to 6 carbon atoms in the alkyl moiety as component (b4).
Mainly of interest are liquid formulations (b) which comprise
(b1) 105 to 25% by weight of a microbicidally active ingredient of the formula (1),
(b2) 10 to 70% by weight of cumenesulfonate,
(b3) 10 to 50% by weight of lactic acid,
(b4) 5 to 75% by weight of 1,2-propanediol and
water to 100%.
The liquid formulations according to the invention are used as active ingredient in cosmetic products, for example deodorants, cleansers, lotions/creams, in household articles, for example as an additive in washing-up liquids, liquid household detergents; as an additive in dental care products, for example in mouthwashs or toothpastes, or as an antimicrobially active ingredient for hard and soft surfaces, for example polymers, paper, textiles and, in particular, the human skin.
The liquid formulations according to the invention are furthermore also suitable as preservatives for cosmetic products and household articles.
They are also used as disinfectants for textile fibre materials.
Liquid formulations according to the invention are prepared by dissolving component (a1) or (b1) in component (a2) or (b4), adding the components (b2) and (b3) to the resulting solution, with stirring, making up the resulting solution with deionized water to 90 to 95% of the final volume, if appropriate adjusting the pH with a cosmetically acceptable base, for example mono- or diethanolamine, and making up the mixture with deionized water to an end volume of 100%.
The dissolved microbicidally active ingredient can be incorporated into cosmetic products and household articles in a trouble free manner. The active ingredient, which is pulverulent per se, is offered to the user in dissolved form. Time-consuming predissolving in suitable solvents while supplying heat is no longer required.
Moreover, the liquid formulations according to the invention are distinguished by a synergistic antimicrobial action (see Example 15) and good storage stability.